ISSN 0965-5441, Petroleum Chemistry, 2007, Vol. 47, No. 3, pp. 201–204. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © L.V. Mel’nik, S.S. Srednev, G.V. Rybina, A.E. Meshechkina, A.S. Shevchuk, A.S. Danilova, 2007, published in Neftekhimiya, 2007, Vol. 47, No. 3, pp. 221–224.
Synthesis of Diols from 1,2-Epoxy-3-butene
L. V. Mel’nik, S. S. Srednev, G. V. Rybina, A. E. Meshechkina,
A. S. Shevchuk, and A. S. Danilova
Yaroslavl State Technical University, Yaroslavl, Russia
e-mail: rybinagv@ystu.ru
Received December 25, 2006
Abstract—The catalytic hydration of 1,2-epoxy-3-butene was studied. The products of the reaction are 3-butenediol-
1,2 (BD-1,2) and 2-butenediol-1,4 (BD-1,4). It was shown that the formation of 2-butenediol-1,4 proceeds predom-
inantly in a polar solvent medium in the presence of the catalytic system “nickel iodide (bromide)–tetraethylammo-
nium iodide” at a temperature of 80°C. In the presence of inorganic acids, the main product is 3-butenediol-1,2.
DOI: 10.1134/S0965544107030085
Glycols have found extensive practical use in many 30 cm3. The reaction mixture was agitated with the use
sectors of the national economy and, in terms of growth of a mechanical rocking chair. Water, solvent, and cat-
in their production rate, rank among the leading prod- alyst were heated in the reactor up to the reaction tem-
ucts of the chemical industry. They are used as solvents, perature, whereupon EB was introduced into the reac-
for the manufacture of softeners and antifreezes, and tor. The progress of the reaction was monitored by fol-
for the syntheses of glycol esters and ethers, polyester lowing the conversion of epoxide determined by direct
resins, and polyurethanes. Hydration of unsaturated titration with perchloric acid [8].
epoxides (e.g., 1,2-epoxy-3-butene) leads to the forma-
The products of the reaction were analyzed using a
tion of unsaturated diols, which possess wide func-
Chrom-5 chromatograph with a flame-ionization detec-
tional capabilities [1]. They exhibit biological activity
tor (a 2.5 × 0.003 m chromatographic column packed
and are used for the manufacture of pharmaceuticals
with PEG-20M-coated diatomite CAW, a temperature
and as monomers for a variety of polymeric materials.
rise from 80 to 195°ë at a rate of 20°C/min, and a car-
rier gas (nitrogen) pressure of 0.45 × 10–5 Pa).
The hydration reaction of unsaturated epoxides was
studied mainly for alicyclic compounds in the presence
The diols obtained were isolated by fractional distil-
of acid catalysts [2, 3, 4]. At the same time, data con-
lation. The boiling point of 3-butenediol-1,2 was
cerning this reaction for acyclic oxides with multiple
96°ë/14 mm Hg, and that of 2-butenediol-1,4 was
bonds are scarce. In [5], it was shown that the hydration
131°ë/13 mm Hg.
of 2,3-epoxypentene-4 yields 4-pentenediol-2,3. In the
case of sulfuric acid-catalyzed hydration of butadiene
monoxide [1], the main product is 3-butenediol-1,2
(BD-1,2). However, the hydration of this epoxide under
certain conditions gives 3-butenediol-1,4 (BD-1,4)
along with diol-1,2 [6, 7], i.e., the hydration reaction
proceeds via two routes. Thus, investigation of the
hydration reaction of 1,2-epoxy-3-butene (EB) is of
both practical and theoretical interest.
Identification of the obtained products was carried
out by means of IR spectroscopy in the region 400–
4000 cm–1 with an IR Fourier RXT instrument and
Spectrum-2000 software. The terminal vinyl double
bond ëç=ëç2 in the spectrum of 3-butenediol-1,2 is
characterized by the stretching vibration band at
1646.86 cm–1, in-plane bending vibrations at 1426 cm−1
δ(ëç), and out-of-plane bending vibrations CH at
928 cm–1 and 993 cm–1. The presence of the hydroxyl
group is characterized by the band of stretching vibra-
tions at 3367.98 cm–1 and bending vibrations of the
C−O group at 1074.11 cm−1. 2-Butenediol-1,4 consists
of the mixture of cis- and trans-isomers. The characteristic
band of C=C stretching vibrations is observed at
1666.42 cm–1, in-plane bending vibration is at 1406.45 cm−1
(C–H-cis) and at 1406.45 cm−1 (C–H-trans), out-
of-plane bending vibrations are at 780 cm–1 (C=C-cis)
and at 976.74 cm–1 (C=C-trans). Stretching vibrations
of the hydroxyl groups are characterized by the band at
The objective of this work was to study the influence
of the type of catalytic system and coordinating solvent
on the direction of the EB hydration reaction.
EXPERIMENTAL
1,2-Epoxy-3-butene was obtained via epoxidation
of 1,3-butadiene with isopropylbenzene hydroperoxide
and isolated by fractional distillation. The mass fraction
of the base substance was at least 96%.
Hydration of EB was carried out in a thermostated, 3369.17 cm–1 (OH group), and bending vibrations are
hermetically sealed glass reactor with a volume of characterized by the band at 1085.89 cm–1 (C–O) [9].
201